Process of mineral concentration



Patented Aug. 9, 1938 UNITED STATES PATENT OFFICE Phosphate Recovery N.Y., a corporation Corporation, New York, of Delaware No Drawing.Application April 27, 1937,

Serial No. 139,210

20 Claims.

The present invention relates to a novel process of concentratingminerals from their ores and is herein described both in connection withmetalliferous ores and in connection with ores of socalled non-metallicminerals, the latter group of ores including materials containing suchminerals as phosphate, calcite, barite, fiuorspar, etc.

In accordance with the inventiomminerals are concentrated from theirores by the use of an insoluble and unsaponifiable oil, together with asulpho-fatty-acid compound produced by the action of a sulphonatingagent on a free unsaturated fatty acid containing at least twelve carbonatoms. Such compounds may, for example, be produced by reaction ofsulphuric acid with such fatty acids as oleic acid, linoleic acid,ricinoleic acid, erucic acid, and other fatty acids of commerce.compound inthe process of the present invention is that of a collectingagent. That is, the sulphofatty-acid compound effects collection of themineral values in cooperation with the insoluble and unsaponifiable oil,which oil promotes the efiiciency of the concentration, as Well as.reduces the quantity of sulpho-fatty-acid compound required. Any one ofvarious hydrocarbon oils can be used as the insoluble and unsaponifiableoil, but fuel oil, on account of its low cost, is usually preferredcommercially.

The aforementioned two agents, namely, the insoluble andunsaponifiable'oil and the sulphofatty-acid compound, are both essentialto the process of the present invention. The insoluble andunsaponifiable oil, when used without the :15 sulpho-fatty-acidcompound, is utterly incapable of achieving concentration. And in theabsence of the insoluble and unsaponifiable oil, the sulpho-fatty-acidcompound, while being capable of operating as a collector, possessesmuch less selectivity, commercial results being in many cases impossibleby means of the sulpho-fattyacid compound alone.

If desired, alkali may also be included among the reagents of theinvention, although in some cases better results are obtained withoutalkali.

The use in mineral concentration of sulphuricacid-reacted organiccompounds as cooperating collecting agents with hydrocarbon oil is notnew in itself. Sulphuric-acid-reacted fatty acid glycerides have beenused in that manner. has also come to my knowledge that minerals can beconcentrated by the combination with hydrocarbon oil of, sulphuric acidesters of aliphatic alcohols. However, in so far as I am aware, noprocess has heretofore been known employing The function of thesulpho-fatty-acid And it hydrocarbon oil in conjunction with compoundsproduced by the action of sulphuric acid on the aforementioned freefatty acids themselves, As I have discovered, this particularcombination of sulphuric-acid-reacted compound with hydrocarbon oil ismuch more effective in mineral concentration than those combinationsemploying reaction products of sulphuric acid with either fatty acidglycerides or with aliphatic alcohols, better recoveries being obtainedwith much smaller reagent quantities.

For certain separations the process of the present invention is alsosuperior to the heretofore known processes employing hydrocarbon oil inconjunction with non-reacted fatty acids or the soaps of these acids.Moreover, the additional use of alkali is usually required in theseprior processes to insure the effectiveness of such fatty acids or fattyacid soaps.

It is understood that the sulpho-fatty-acid compound employed in theprocess of the present invention should be used in the proper amountrelative to that of the insoluble and unsaponifiable oil to causecollection to be conjointly effected by these two agents. In each of theexamples hereinafter given, substantially no effect would be obtainedfrom the sulpho-fatty-acid compound, in so far as collection isconcerned, if employed under the particular conditions described inamount substantially smaller than that indicated. In practice, ofcourse, simple experimental tests are necessary to determine the reagentamounts in each individual case, it being a well-known fact that eachset of conditions, including the ore treated, presents its own problemas to the exact quantities of reagents to be used.

The sulpho-fatty-acid compounds of the present invention may be used inthe form of the crude reaction mixtures obtained by adding, withstirring, concentrated sulphuric acid (of a specific gravity of about 66Be.) in various proportions to the corresponding unsaturated fatty acidsselected. The ensuing reaction causes a rise in temperature, theresultant product being more viscous than the original free fatty acid.This material is allowed to cool to room temperature, stirring thewhile. In this state it is ready for use as a collector without furthertreatment. If desired, however, it may first be neutralized by asubstance having an alkaline reaction in water, such as sodiumhydroxide, pyridine, etc. This neutralization may be either partial, asindicated by methyl orange, or complete, as indicated byphenolphthalein, the alkaline substance in either case being added inthe presence of the indicating substance until completion of the desiredreaction is shown by the color change. Partial neutralization, asindicated by methyl orange, probably results in neutralizing thesulphur-containing acid radical only, whereas complete neutralization,as indicated by phenolphthalein, may result in neutralizing both thesulphur-containing acid radical and the carboxyl group.

The invention is, of course, not limited to any specific method ofpreparing the sulpho-fattyacid compound required for use in its process.Any appropriate sulphonating agent which is the equivalent of sulphuricacid can be used instead of that acid for producing thesulphur-containing acid radical, it being understood that the termsulphonating is used herein without reference to the character of thatradical.

In preparing the ore for treatment by the proces of the invention, it isin general desirable that it be comminuted to a particle size mostsuitable for efllcient operation and that it be largely deslimed, itsdesliming greatly minimizing the consumption of the reagents.Ordinarily, the crude ore is first subjected to. a preliminary grindingoperation and thereafter screened or classified to remove all particlesother than those desired. The undersize may then be deslimed, and theoversize reground, deslimed, and added to the deslimed undersize; or theoversize may be reground, added to the undeslimed undersize, and thewhole then deslimed. I

Subsequent to mixing the ore-with the reagents, the actual step ofseparating the mineral values may be effected by any desired form ofphysical concentration, such as froth flotation, tabling, hydraulicclassification, etc. In froth flotation, any suitable irother may beadded to the ore along with the other reagents.

The following examples described certain tests which have been made incarrying the invention into eflect, the reagent proportions in eachbeing figured on the basis of the dry weight tonnage (2,000 lbs.) of thematerial treated.

EXAMPLE 1 To a commercial brand of oleic acid, known as red oil, wasadded, with stirring, 5% of its weight of concentrated sulphuric acid.The temperature of the mixture was observed to rise. stirring beingcontinued until the original temperature was restored. This reactionmixture containing sulpho-oleic-acid was used in the following test:

Deslimed phosphate feed to plant No. 4 of the Phosphate RecoveryCorporation in Florida, consisting mainly of so-called bone phosphate oflime (tri-calcium phosphate) and silica, and of a particle size to pass28-mesh, was made up with water into a thick pulp of about 70% solids.To this pulp were added, during agitation in an impeller-type mixer, 0.5lb. per ton of caustic soda, 2.78 lbs. per ton of fuel oil, 1.28 lbs.per ton of the sulphuric-acid-reacted oleic acid product prepared asabove-described, and 0.14 lb. per ton of a frothing agent consisting of3 parts of crude rosin residue dissolved in 1 part of kerosene. Thisaddition of reagents required one minute, subsequent to which agitationwas continued in the mixer for two more minutes. The pulp thusconditioned was transferred to a laboratory subaeration' flotationmachine where in a diluted state it was agitated for one minute. duringwhich a rougher concentrate was floated and collected. Upon removal ofthe tailing, the rougher concentrate was returned to the flotationmachine where, without further addition of reagents, it was againtreated for another period of one minute, a final concentrate being thusobtained. The tailing of this cleaning upon separate analysis was foundto constitute a middling, which in commercial operation would bereturned to the flotation cells for further extraction of values.

The results of the test were as follows:

Percent assay P Percent "cent Product weight r eco ye y B. P. L. Ins.

100.0 40. 71 100.0 49.6 76. Gil S 96 93. 4 4. 0 20. 47 2. 0 46. 4 i. 034. (l

Comparative test 1 The same feed was taken and the same procedures werefollowed as in Example 1, but the sulphuric-acid-reacted oleic acidproduct was omitted and, instead, Turkey-red oil (a partly neutralizedreaction product of castor oil with sulphuric acid) was employed. Asmuch as 4 lbs. per ton of this material was required, along with thesame amounts of caustic soda, fuel oil, and kerosene-rosin 'frothingagent, to achieve the concentration indicated in the following table:

Percent assay Percent Product :55,? recovery B. P. L Ins.

Comparative test 2 Here, sodium lauryl sulphate, in the amount of 5 lbs.per ton, was employed instead of the sulphuric-acid-reacted oleic acidproduct of Example 1. The conditions of the test were otherwise the sameas in that example, including the feed and the amounts of caustic soda,fuel oil, and kerosene-rosin frothing agent, the results being asfollows:

For the purpose of this example, no alkali was employed. A thick pulp ofthe same feed as before was conditioned with 2.78 lbs. of fuel oil, 1.28lbs. of sulphurlc-acid-reacted oleic acid material, and 0.14 lb. ofkerosene-rosin frothing agent, all per ton of dry feed. The procedureswere otherwise identical to those of Example the sulphuric-acid-reactedoleic acid material and kerosene-rosin frothlng agent being obtained inthe same way. The results or the were as follows:

test

Percent assay Percent Product 551 recovery I B. P. L. Ins.

Comparative test 3 I With 4 lbs. per ton of Turkey-red oil replacing thesulphuric-acid-reacted oleic acid material in Example 2, all otherconditions being the same, including the feed and the amounts of fueloil and kerosene-rosin frothing agent, the following results wereobtained:

Percent assay Percent Product 35%;? u recovery 13. P. L. Ins.

Comparative test! A thick pulp of the same feed as before was agitatedin the mixer with 5 lbs. per ton of sodium lauryl sulphate, togetherwith the same amounts of fuel oil and kerosene-rosin frothing agent asin Example 2. Subsequently treating the pulp in the flotation machine,no flotation whatever could be effected EXAMPLE 3 ton of the abovepartly neutralized sulphuricacid-reacted oileic acid product. In theusual manner the pulp was thereafter diluted and agitated in theflotation machine to yield a rougher concentrate, which upon removal ofthe tailing was retreated without further addition of reagents, yieldinga final concentrate and a mid-= dling,

The results of the test were as follows:

Percent assay Percent Product perpent recovery weight B B. P. L Ins.

EXAMPLE 4 Employing the same feed as before, the procedures of Example 3were repeated, but with the omission of caustic soda in the flotationtest. Also, the sulphuric-acid-reacted oleic acid product was in thisinstance employed in a state of complete neutralization, theneutralizing medium being caustic soda, which was added to the materialresulting from the initial reaction with sulphuric acid in the presenceof phenolphthalein as an indicator. The final concentrate assayed 77.55%B. P. L., the B. P. L. recovery therein being 88.3%.

EXAMPLE 5 Here, red oil was treated with sulphuric acid in the samemanner as in Example 3, but the resulting material was thereafter partlyneutralized with pyridine, employing methyl orange as an indicator. Inthe subsequent test 2 lbs. per ton of this product, together with 0.5lb. per ton of caustic soda and 2.78 lbs. per ton of fuel oil, wereemployed, the procedures being otherwise the same as before, the samefeed being taken.

The B. P. L. assay of the concentrate was 75.56% andthe B. P. L.recovery therein 90.5%.

Examine 6 The conditions of this test were identical in every respect tothose of Example 5, except that no caustic soda was used. A concentratewas obtained assaying 74.76% B. P. L., 95% B. P. L. being recoveredtherein.

As can be readily seen from the preceding examples and comparativetests, the sulphuricacid-reacted oleic acid of this invention, with orwithout prior treatment with alkali and in spite of the much smallerquantities used, gives far superiorresults than either the Turkey redoil or the sodium lauryl sulphate used in other processes with which Iam familiar.

EXAMPLE 7 In this instance sulphuric-acid-reacted oleic acid was usedwithout prior treatment with alkali and with no other agents than fueloil. A thick pulp of the same feed as before was agitated in the mixerwith 3 lbs. per ton of fuel oil and i 2.1 lbs. per ton ofsulphuric-acid-reacted oleic acid product prepared as in Example 1.Thereafter, the pulp was treated in the flotation machine for theproduction of a. rougher concentrate which, upon removal of the tailing,was retreated without further addition of reagents, yielding a finalconcentrate and a middling. The results of this test were as follows:

Percent assay Percent; Product wggfi recovery B. P. L Ins.

Comparative test 5 Employing the same feed as before, the procedures ofExample 7 were repeated omitting the use of fuel oil, thesulphuric-acid-reacted oleic acid product being used alone and in thesame amount, namely, 2.1 lbs. per ton. A final concentrate was obtainedassaying 65.42% B. P. L.,

' the B. P. L. recovered therein being only 65.4%.

Comparative test 6 The conditions of this test were identical to thoseof comparative test 5, except that the sulphuric-acid-reacted oleic acidproduct was used in the increased amount of 5.05 lbs. per ton. A B. P.L. recovery of 94.6% was effected in the final concentrate, but the B.P. L. grade of that concentrate was only 50.07%.

Comparative test 7 A thick pulp of the same feed as before was agitatedin the mixer with no other agent than fuel oil, which was used in thesame amount as in Example '1, namely, 3 lbs. per ton. Subsequentlytreating the pulp in the flotation machine, no flotation whatever couldbe eflected.

Comparative test 8 Under the same conditions as in comparative test '1,but with the amount of fuel oil increased to as much as 50 lbs. per ton,still no flotation could be effected in the flotation machine.

Comparative test 9 For the purpose of this example a different phosphatefeed was taken, namely, that to the V Florida plant of Swift andCompany, also largely deslimed, but of a much lower grade of phosphate.A thick pulp of this feed was agitated with 2 lbs. of fuel oil and 2lbs. of sulphuric-acidreacted oleic acid material, both per ton of dryfeed. Here, the sulphuric-acid-reacted oleic acid material was obtainedby treatment of red oil with 25% of its weight of concentrated sulphuricacid. Subsequent to the conditioning indicated, the pulp was processedin the flotation machine in the same manner as before, the followingresults being obtained:

Percent Percent Product at 'ggg recovery B. P. L Ins. L

100. 27. 45 100.0 27. 8 75. 06 7. 13 76. 0 7. s as. 87 9. 8 6i. 9 5. 9914. 2

EXAMPLE 9 The same feed as in Example 8 was taken and the sameprocedures as before were followed, but in this instance conditioningwas carried out with 0.4 lb. per ton of caustic soda, together with the2 lbs. per ton of fuel oil and 2 lbs. per ton of sulphuric-acid-reactedoleic acid material, the latter agent being prepared in the same manneras in that example. The final concentrate assayed 71.84% B. P. L., theB. P. L. recove therein being 70.5%.

Comparative test 10 This test was carried out for comparison withExamples 8 and 9. Employing the same feed as in those examples, with athick pulp thereof were admixed 1.5 lbs. of caustic soda, 5.5 lbs. offuel oil, 1.5 lbs. of free fatty acid from fish oil. and 0.14 lb. of thekerosene-frothing agent previously described, allper ton of dry feed.The subsequent flotation procedures were the same as before and yieldedthe results shown in the table below, it being especially noted that theB. P. L. recovery in the final concentrate was much lower than in eitherof Examples 8 and 9:

Percent eeeay PM Product mg recovery 3.9.1. Ins.

100.0 .67 1%.0 25.6 71.74 11.27 04.1 8.0 .62 7.1 00.4 44 ass EXAMPLE i0Linoleic acid was treated with of its weight of concentrated sulphuricacid, the mixture being stirred until cool. A thick pulp of the samefeed as in Example 1 was conditioned with 0.27 lb. per ton of thisproduct, together with 0.4 lb. per ton of caustic soda, 4 lbs. per tonof fuel oil, and 0.14 lb. per ton of the kerosenerosin frothing agentpreviously described, the subsequent flotation procedures being the sameas before and yielding the following results:

. Percent assay Percent Product Egg recovery 13. P. 1.. Ins.

100. 0 40. 29 100. 0 42. 1 80.18 2 86 Y 83. 8 3. 9 69. 28 6. 6 Tail 64.0 7. 88 l0. 6

Examine 11 Ricinoleic acid was treated with 5% of its weight ofconcentrated sulphuric acid, the mixture being stirred until cool. Inthe subsequent test 1.33 lbs. per ton of this product were employed,together with 0.6 lb. per ton of caustic soda, 2.66 lbs. per ton of fueloil, and 0.14 lb. per ton of the kerosene-frcthing agent previouslydescribed, the test being carried out on the same feed as in Example 1.All other conditions were the same as before, the results being asfollows:

' Percent assay Percent Product Exam recovery is. P. L. Ins. P

100. 0 30. 33 100. U 41. 7 77. 67 4 78 82. 4 a. 4 45. 01 0. c 49. 9 6.29 8. 0

Exauru: 12

The same feed as in Example 1 was taken and the same procedures as inExample 11 were followed, but the caustic soda was omitted and theamount of sulphuric-acid-reacted ricinoleic acid product was increasedto 3.5 lbs. per ton, the following results being obtained:

Percent assay P crcent Product recovery B. P. L Ins.

EXAMPLE 13 Erucic acid, a solid at normal temperatures, was melted andthereafter treated with 5% of its weight of concentrated sulphuric acid,stirring of the mixture being carried out until cool. The resultingproduct was then dissolved in an equal part by weight of fuel oil, whichsolution was used as follows:

' A thick pulp of the same feed as in Example 1 was agitated in themixer with 0.6 lb. per ton of caustic soda, an amount of the above fueloil solution corresponding to 1.27 lbs. per ton of thesulphuric-acid-treated material dissolved therein, an additional amountof fuel oil to bring its total up to 2.71 lbs. per ton, and 0.14 lb. perton of the kerosene-rosin frothing agent previously described.Subsequently, the pulp was processed in the flotation machine in thesame manner as before.

The results of this test were as follows:

Percent assny Percent Product 522 recovery 1;. P. L. Ins. R L

100. 0 39. 29 100. 0 48. 2 77. 17 4. 98 94. 7 3. 8 21. 8O 2. 1 Tail 48.0 2. 61 l 3. 2

EXAMPLE 14 A synthetic limestone ore containing about 30% calciumcarbonate to 70% quartz, all finer than 28-mesh, was made up with waterinto a pulp of 70% solids, which pulp was agitated in the mixer with 0.5lb. of caustic soda, 2.66 lbs. of fuel oil, 2.4 lbs. ofsulphuric-acid-reacted oleic acid material, and 0.14 lb. of thekerosenerosin frothing agent previously described, all per ton of dryfeed, the sulphurio-acid-reacted oleic acid material being obtained asin Example 3. As before, the reagents were added during agitation, whichaddition required one minute, the total period of agitation being threeminutes. Subsequent to the conditioning indicated, the pulp was dilutedand agitated in'the flotation machine for the production of a rougherconcentrate which, upon removal of the tailing, was again subjected totreatment in the machine, yielding a final concentrate and a middling.As

before, the frothing period in each of the two operations was oneminute, the cleaning operationbeing carried out without further additionof reagents. The results of this test were as follows:

Percent Percent Percent Product assay recovery welght C8000 C5003EXAMPLE 15 Valley Forge Cement Companys "Classifier Sands were made, upwith water into a pulp.

Percent recovery Ca 0 Os Percent assay GaCOa Percent Product weight wasComparative test 11 Percent recovery 00.000

Percent Product weight coho EXAMPLE 16 Barlte ore obtained from thePage. Mining Company of Cartersville, Georgia, and known as "Jig Hutchproduct, was sized on a 28-mesh screen. The oversize was ground to passthrough the same screen, the total sample being then deslimed and formedinto a pulp of 70% solids. This pulp was agitated in the mixer with 0.3lb. per ton of caustic soda, 3 lbs. per ton of fuel oil, 1.2 lbs. perton of sulphuric-acid-reacted oleic acid product prepared as in Example3, and 0.14 lb. per ton of the kerosene-rosin frothing agent previouslydescribed, the total period of agitation being three minutes includingthe time for addition of the reagents, which was one minute.

Subsequent to the conditioning indicated, the pulp was treated in theflotation machine as before for one minute, during which a rougherconcentrate was separated. Here, upon removal of the tailing, therougher concentrate was three times retreated in the machine, yielding afinal concentrate and three middlings. For each of these cleaningoperations the frothing period was one minute, no further addition ofreagents being made. The results of this test are indicated in thefollowing table, wherein middlingl is the tailing of the first cleaningoperation, middling 2 is the tailing of the second cleaning operation,and middling 3 is the tailing of the third cleaning operation:

Percent dis- Percent Percent assay tribution, Product weight BaSO s10,easo, s10,

EXAMPLE 17 Barite ore from Sweetwater, Tennessee, was put through a35-mesh screen, deslimed, and formed into a pulp of 70% solids. To thispulp were added, during agitation in the mixer, 0.8 lb. of caustic soda,2.66 lbs. of fuel oil, 1.6 lbs. of sulphuric-acid-reacted oleic acidproduct prepared as in Example 1, and 0.14 lb. of the kerosene-rosinfrothing agent previously described, all per ton of dry feed. Theaddition period was one minute, subsequent to which agitation wascontinued for two more minutes. The pulp thus conditioned was dilutedand agitated in the flotation machine for one minute, a rougherconcentrate being obtained which, upon removal of the tailing, was twiceretreated in the machine, without further addition of reagents, yieldinga final concentrate and two middlings, each retreatment requiring aboutone minute. The results of the test are shown in the following table,middling 1 being the tailing of the first retreatment and middling 2being the tailing of the second retreatment:

Percent Percent Percent Product assay recovery B8804 assoi Comparativetest 12 without desliming. To this pulp were added, during agitation inthe mixer, 0.5 lb. of caustic soda, 1 lb. of fuel oil, 2 lbs. ofsulphuric-acidreacted olelc acid product prepared as in Example 3, and0.14 lb. of the kerosene-rosin frothing agent previously described, allper ton of dry feed. This addition required one minute. subsequent towhich agitation was continued for two more minutes. diluted and agitatedin the flotation machine for ten minutes, a rougher concentrate beingseparated which, upon removal of the tailing, was again treated in themachine for ten minutes, without further addition of reagents, yieldinga final concentrate and a middling. The results of the test were asfollows:

The procedures of Example 17 were repeated Pewentasw 9mm on the samebarite ore with the sulphuric-acid- F od t 23: 9: 1: reogvery reactedoleic acid product omitted, 1.6 lbs. per 011 F610: ton of Turkey-red oilbeing used instead, along with the same amounts of caustic soda, fueloil, 100.0 1.05 4.33 100.0 and kerosene-rosin frothing agent. Theresults 3H8 in this instance were as follows: 931s 0.38 1:88 3413Product zfj fl 3:52:? raj??? EXAMPLE 20 a 4 a Oxidized copper ore fromthe Utah Copper Company, containing azurite and malachite, was FM %:33&2? ground to minus 65-mesh, the ground ore being d -2 9 -5 firstdeslimed and thereafter formed into a pulp 13;; 2%,? {3;} of 70% solids.This pulp was agitated in the mixer with 0.5 lb. per ton of causticsoda, 1 1b.

Examrm: 18

A thick pulp of fiuorspar ore from the slime pond tailing of theRosiclare plants of the Hillside Fluorspar Company, Illinois, containingas gangue constituents both silica and. calcite, was agitated in themixer with 0.26 lb. of sulphuric acid-reacted oleic acid productprepared as in Example 3, 0.44 lb. of fuel oil, and 0.14 lb. of thekerosene-rosin frothing agent previously described, all per ton of dryfeed, the total period of agitation being three minutes including thetime for adding the reagents, which was one minute. Subsequently, thepulp was diluted and agitated in the flotation machine for one minute, arougher concentrate being separated which, upon removal of the tailing,was three times retreated in the machine, without further addition ofreagents, yielding a final concentrate and three middlings, the frothingperiod for each of the retreatments being about one minute. The resultsare shown in the following table, wherein middling 1 is the tailing ofthe first retreatment, middling 2 is the tailing of the secondretreatment, and middling 3 is the tailing of the third retreatment:

recovery Percent weight Product CaCO: S10:

Exmrn 19 Low grade copper sulphide ore from Utah was ground to minus65-mesh, the ground ore being made up with water into a pulp of 70%solids,

per ton of fuel oil, 1.67 lbs. per ton of sulphuricacid-reacted oleicacid product prepared as in Example 3, and 0.14 lb. per ton of thekerosenerosin frothing agent previously described, the total period ofagitation being three minutes including the time for adding thereagents, which was one minute. Subsequently, the pulp was diluted andagitated in the flotation machine for one and one-half minutes, yieldinga rougher concentrate which, upon removal of the tailing, was threetimes retreated in the machine, on each occasion for one and one-halfminutes, without further addition of reagents, a final concentrate andthree middlings being obtained by these cleaning operations. The resultsare indicated in the following table, wherein middling 1 is the tailingof the first cleaning operation, middling 2 is the tailing of the secondcleaning operation, and middling 3 is the tailing of the third cleaningoperation:

Percent Percent Product zig ag assay recavlery 100. 2. 100. 0 6. 0 28.44 82. 0 l. 9 6. 05 6. 3 3. 0 2. 27 4. 4' l0. 6 0. 47 2. 4 77. 7 0. l34. 9

Exam? 21 The pulp thus conditioned was Percent recovery Cu Percent assayCu Percent Product weight Hid PNPFN It has also been found that thealuminum silicate mineral known as kyanite may be floated by the processof the present invention.

The applicability of the process of the invention to tabling is shown bythe following example.

i EXAMPLE 22 The same deslimed phosphate feed as in Example l was taken,a sample of this feed being made up with water into a pulp oi 70%solids. To this pulp were added, during agitation in the mixer, 0.8 lbs.per ton of caustic soda, 6.66 lbs. per ton of fuel oil, and 8.42 lbsQperton oi? sulphuric-acid-reacted oleic acid product prepared as inExample 1. The addition period was one minute, subsequent to whichagitation was com tinued for two minutes more. Thereafter, the pulp wasfed to a laboratory-size Wilfley table over a period of one minute, withthe following results:

Percent Comparative test 13 1 Percent assay Percent Product 3:55:: 1recovery B. P. L. Ins.

None of ,the detailed procedures described herein should be interpretedas limiting the invention, these procedures being capable of beingmodified in many ways without departing from its spirit.

What is claimed is:

1. A process of concentration comprising admixing an ore with aninsoluble and unsaponifiable oil and a sulpho-fatty-acid compoundproduced by the action of a sulphonating agent on a free unsaturatedfatty acid of at least twelve carbon atoms, and separating in an aqueouspulp the mineral values from the ore, said oil and sulpho-fatty-acidcompound being used in relative amounts to cause them to conjointlyeffect collection of said values.

2. A process of concentration comprising ad-- mixing an ore with aninsoluble and unsaponifiable oil and a sulpho-fatty-acid compoundproduced by the action of a sulphonating agent on a free unsaturatedfatty acid of at least twelve carbon atoms, said sulpho-fatty-acidcompound being at least in part neutralized by a substance having analkaline reaction in water, and separating in an aqueous pulp themineral values from the ore, said oil and sulpho-fatty-acid compoundbeing used in relative amounts to cause them to conjointly effectcollection of said values.

3. A process of concentration comprising admixing an ore with aninsoluble and unsaponifiable oil and the reaction mixture obtained byreacting'a sulphonating agent with a free unsaturated fatty acid of atleast twelve carbon atoms, and separating in an aqueous pulp themineral, values from the ore, said oil and reaction mixture being usedin relative amounts to cause them to conjointly efiect collection ofsaid values.

4. A process of concentration comprising admixing an ore with aninsoluble and unsaponifiable oil and the reaction mixture obtained byreacting a sulphonating agent with a free unsaturated fatty acid of atleast twelve carbon atoms, said reaction mixture being used in a stateof at least partial neutralization by a substance having an alkalinereaction in water, and separating in an aqueous pulp the mineral valuesfrom the ore, said oil and reaction mixture being used in relativeamounts to cause them to conjointly effect collection of said values.

5. A process of concentration comprising admixing an ore with aninsoluble and unsaponifiable oil and a sulpho-fatty-acid compoundproduced by the action of sulphuric acid on a free unsaturated fattyacid of at least twelve carbon atoms, and separating in an aqueous pulpthe mineral values from the ore, said oil and sulphofatty-acid compoundbeing used in relative amounts to cause them to conjointly effectcollection of said values.

6. A process of concentration comprising ad mixing an ore with aninsoluble and unsaponifiable oil and the reaction mixture obtained byreacting sulphuric acid with a free unsaturated fatty acid of at leasttwelve carbon atoms, and

separating in an .aqueous pulp the mineral'values from the ore, said oiland reaction mixture being used in relative amounts to cause them toconjointly effect collection of said values.

7. A process of concentration comprising admixing an ore with aninsoluble and unsaponifiable oil, a sulpho-fatty-acid compound producedby the action of a sulphonating agent on a free unsaturated fatty acidof at least twelve carbon atoms, and an alkali, and separating in anaqueous pulp the mineral values from the ore, said oil andsulpho-fatty-acid compound being used in relative amounts to cause themto conjointly efiect collection of said values.

8. A process of concentration comprising admixing an ore with aninsoluble and unsaponifiall able oil and a sulpho-iatty-acid compoundproduced by the action of a sulphonating agent on a free unsaturatedfatty acid of at least twelve carbon atoms, and concentrating themineral values from the pulp by froth flotation, said oil andsulpho-fatty-acid compound being used in relative amounts to cause themto conjointly effect collection of said values.

10. A process of concentration comprising agitating an aqueous pulp ofsuitably divided particles of an ore with an insoluble andunsaponiflable oil and the reaction mixture obtained by reactingsulphuric acid with a free unsaturated fatty acid of at least twelvecarbon atoms, and concentrating the mineral values from the pulp byfroth flotation, said oil and reaction mixture being used in relativeamounts to cause them to conjointly eifect collection of said values.

11. A process of concentration comprising admixing an ore containing anon-metallic mineral with an insoluble and unsaponiflable oil and asulpho-fatty-acid compound produced by the action of a sulphonatingagent on a free unsaturated fatty acid of at least twelve carbon atoms,and separating in an aqueous pulp the non-metallic'mineral values fromthe ore, said oil and sulpho-iatty-acid compound being used in relativeamounts to cause them to conjointly effect collection of said values.

12. A process of concentration comprising admixing an ore containing anon-metallic mineral with an insoluble and unsaponifiable oil and thereaction mixture obtained by reacting sulphuric acid with a freeunsaturated fatty acid of at least twelve carbon atoms, and separatingin an aqueous pulp the non-metallic mineral values from the ore, saidoil and reaction mixture being used in relative amounts to cause them toconjointly efiect collection of said values.

13. A process of concentration comprising admixing an ore containingphosphate with an insoluble and unsaponifiable oil and asulpho-fattyacid compound produced by the action of a sulphonating agenton a free unsaturated fatty acid of at least twelve carbon atoms, andseparating in an aqueous pulp the phosphate values from the ore, saidoil and sulpho-fatty-acid compound being used in relative amounts tocause them to conjointly effect collection of said values.

to cause them to conjointly effect collection of said values.

15. A process of concentration comprising admixing an ore containingbarite with an insoluble and unsaponiflable oil and a sulpho-fatty-acidcompound produced by the action of a sulphonating agent or afreeunsaturated fatty acid of at least twelve carbon atoms, andseparating in an aqueous pulp the barite values from the ore, said oiland sulpho-fatty-acid compound being used in relative amounts to causethem to conjointly effect collection of said values.

16. A process of concentration comprising admixing an ore containingbarite with an insoluble and unsaponifiable oil and the reaction mixtureobtained by reacting sulphuric acid with a free unsaturated fatty acidof at least twelve carbon atoms, and separating in an aqueous pulp thebarite values from the ore, said oil and reaction mixture being used inrelative amounts to cause them to conjointly effect collection of saidvalues.

17. A process of concentration comprising admixing an oracontainingcalcite with an insoluble and unsaponifiable oil and a sulpho-fattyacidcompound produced by the action of a sulphonating agent on a freeunsaturated fatty acid of at least twelve carbon atoms, and separatingin an aqueous pulp the calcite values from the ore, said oil andsulpho-fatty-a'cid compound being used in relative amounts to cause themto conjointly efiect collection of said values.

18. A process of concentration comprising admixing an ore containingcalcite with an insoluble and unsaponifiable oil and the reactionmixture obtained by reacting sulphuric acid with a free unsaturatedfatty acid of at least twelve carbon atoms, and separating in an aqueouspulp the calcite values from the ore, said oil and reaction mixturebeing used in relative amounts to cause them to conjointly effectcollection of said values.

19. A process of concentration comprising admixing an ore with aninsoluble and unsaponiflable oil and a. sulpho-oleic-acid compoundproduced by the action of a sulphonating agent on oleic acid andseparating in an aqueous pulp the mineral values from the ore, said 011and sulpho-oleic-acid compound being used in relative amounts to causethem to conjointly eifect collection of said values.

20. A process of concentration comprising admixing an ore with aninsoluble and unsaponifiable oil and the reaction mixture obtained byreacting sulphuric acid with oleic acid, and separating in an aqueouspulp the mineral values from the ore; said oil and reaction mixturebeing used in relative amounts to cause them to conjointly efiectcollection of said values.

' FRANCIS X. TARTARON.

CERTIFICATE OF CORRECTION.

Patent No. 2,126,292. August 9, 19 v FRANCIS x.. TARTARON.

It is hereby certified that error, appears in the printed specificationof the above numbered patent requiring correction as follows: Page 5second column, line 17, for "90 5%" read 96. 5%; and that the saidLetters Patent shouldbe read with this correction therein that the samemay conform to th record of the case in the Patent Office. I

Signed and sealed. this 20th day of September, A. D. 195

Henry Van Arsdale (Seal) I Acting Commissioner of Patents.

